Enhanced Hydrogen Generation by Reverse Spillover Effects over Bicomponent Catalysts

Overview

Journal Nat Commun

Specialty Biology

Date 2022 Jan 11

PMID 35013274

Authors

Zhe Gao

Guofu Wang

Tingyu Lei

Zhengxing Lv

Mi Xiong

Liancheng Wang

Shuangfeng Xing

Jingyuan Ma

Zheng Jiang

Yong Qin

Affiliations

Soon will be listed here.

Abstract

The contribution of the reverse spillover effect to hydrogen generation reactions is still controversial. Herein, the promotion functions for reverse spillover in the ammonia borane hydrolysis reaction are proven by constructing a spatially separated NiO/AlO/Pt bicomponent catalyst via atomic layer deposition and performing in situ quick X-ray absorption near-edge structure (XANES) characterization. For the NiO/AlO/Pt catalyst, NiO and Pt nanoparticles are attached to the outer and inner surfaces of AlO nanotubes, respectively. In situ XANES results reveal that for ammonia borane hydrolysis, the H species generated at NiO sites spill across the support to the Pt sites reversely. The reverse spillover effects account for enhanced H generation rates for NiO/AlO/Pt. For the CoO/AlO/Pt and NiO/TiO/Pt catalysts, reverse spillover effects are also confirmed. We believe that an in-depth understanding of the reverse effects will be helpful to clarify the catalytic mechanisms and provide a guide for designing highly efficient catalysts for hydrogen generation reactions.

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References

Lu D, Li J, Lin C, Liao J, Feng Y, Ding Z . A Simple and Scalable Route to Synthesize Co Cu Co O @Co Cu Co O Yolk-Shell Microspheres, A High-Performance Catalyst to Hydrolyze Ammonia Borane for Hydrogen Production. Small. 2019; 15(10):e1805460. DOI: 10.1002/smll.201805460. View

Li J, Guan Q, Wu H, Liu W, Lin Y, Sun Z . Highly Active and Stable Metal Single-Atom Catalysts Achieved by Strong Electronic Metal-Support Interactions. J Am Chem Soc. 2019; 141(37):14515-14519. DOI: 10.1021/jacs.9b06482. View

Xiong M, Gao Z, Zhao P, Wang G, Yan W, Xing S . In situ tuning of electronic structure of catalysts using controllable hydrogen spillover for enhanced selectivity. Nat Commun. 2020; 11(1):4773. PMC: 7508871. DOI: 10.1038/s41467-020-18567-6. View

Hess N, Bowden M, Parvanov V, Mundy C, Kathmann S, Schenter G . Spectroscopic studies of the phase transition in ammonia borane: Raman spectroscopy of single crystal NH3BH3 as a function of temperature from 88 to 330 K. J Chem Phys. 2008; 128(3):034508. DOI: 10.1063/1.2820768. View

Dresselhaus M, Thomas I . Alternative energy technologies. Nature. 2001; 414(6861):332-7. DOI: 10.1038/35104599. View

Yao Q, Shi Y, Zhang X, Chen X, Lu Z . Facile Synthesis of Platinum-Cerium(IV) Oxide Hybrids Arched on Reduced Graphene Oxide Catalyst in Reverse Micelles with High Activity and Durability for Hydrolysis of Ammonia Borane. Chem Asian J. 2016; 11(22):3251-3257. DOI: 10.1002/asia.201601147. View

Gudmundsdottir S, Skulason E, Jonsson H . Reentrant mechanism for associative desorption: H2/Pt(110)-(1×2). Phys Rev Lett. 2012; 108(15):156101. DOI: 10.1103/PhysRevLett.108.156101. View

Kresse , Furthmuller . Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys Rev B Condens Matter. 1996; 54(16):11169-11186. DOI: 10.1103/physrevb.54.11169. View

Karim W, Spreafico C, Kleibert A, Gobrecht J, VandeVondele J, Ekinci Y . Catalyst support effects on hydrogen spillover. Nature. 2017; 541(7635):68-71. DOI: 10.1038/nature20782. View

10.

Wang S, Zhang D, Ma Y, Zhang H, Gao J, Nie Y . Aqueous solution synthesis of Pt-M (M = Fe, Co, Ni) bimetallic nanoparticles and their catalysis for the hydrolytic dehydrogenation of ammonia borane. ACS Appl Mater Interfaces. 2014; 6(15):12429-35. DOI: 10.1021/am502335j. View

11.

Wang N, Sun Q, Bai R, Li X, Guo G, Yu J . In Situ Confinement of Ultrasmall Pd Clusters within Nanosized Silicalite-1 Zeolite for Highly Efficient Catalysis of Hydrogen Generation. J Am Chem Soc. 2016; 138(24):7484-7. DOI: 10.1021/jacs.6b03518. View

12.

Perdew , Burke , Ernzerhof . Generalized Gradient Approximation Made Simple. Phys Rev Lett. 1996; 77(18):3865-3868. DOI: 10.1103/PhysRevLett.77.3865. View

13.

Zhang J, Gao Z, Wang S, Wang G, Gao X, Zhang B . Origin of synergistic effects in bicomponent cobalt oxide-platinum catalysts for selective hydrogenation reaction. Nat Commun. 2019; 10(1):4166. PMC: 6744570. DOI: 10.1038/s41467-019-11970-8. View

14.

Kalidindi S, Indirani M, Jagirdar B . First row transition metal ion-assisted ammonia-borane hydrolysis for hydrogen generation. Inorg Chem. 2008; 47(16):7424-9. DOI: 10.1021/ic800805r. View

15.

Sun Q, Wang N, Xu Q, Yu J . Nanopore-Supported Metal Nanocatalysts for Efficient Hydrogen Generation from Liquid-Phase Chemical Hydrogen Storage Materials. Adv Mater. 2020; 32(44):e2001818. DOI: 10.1002/adma.202001818. View

16.

Tedsree K, Li T, Jones S, Chan C, Yu K, Bagot P . Hydrogen production from formic acid decomposition at room temperature using a Ag-Pd core-shell nanocatalyst. Nat Nanotechnol. 2011; 6(5):302-7. DOI: 10.1038/nnano.2011.42. View

17.

Gao Z, Qin Y . Design and Properties of Confined Nanocatalysts by Atomic Layer Deposition. Acc Chem Res. 2017; 50(9):2309-2316. DOI: 10.1021/acs.accounts.7b00266. View

18.

Jiang L, Liu K, Hung S, Zhou L, Qin R, Zhang Q . Facet engineering accelerates spillover hydrogenation on highly diluted metal nanocatalysts. Nat Nanotechnol. 2020; 15(10):848-853. DOI: 10.1038/s41565-020-0746-x. View

19.

Ren X, Lv H, Yang S, Wang Y, Li J, Wei R . Promoting Effect of Heterostructured NiO/Ni on Pt Nanocatalysts toward Catalytic Hydrolysis of Ammonia Borane. J Phys Chem Lett. 2019; 10(23):7374-7382. DOI: 10.1021/acs.jpclett.9b03080. View

20.

Joo J, Dillon R, Lee I, Yin Y, Bardeen C, Zaera F . Promotion of atomic hydrogen recombination as an alternative to electron trapping for the role of metals in the photocatalytic production of H2. Proc Natl Acad Sci U S A. 2014; 111(22):7942-7. PMC: 4050604. DOI: 10.1073/pnas.1405365111. View